The effect of collisions in the multiphoton decomposition of chloroform-d
Abstract
The multiphoton decomposition (MPD) of chloroform-d, CDCl3, with a pulsed 13CO2 infrared laser is reported. A new method is developed that takes into account the effect of the number of pulses required to obtain a measurable decomposition. This method relies on difference equations and replaces current methods based on differential calculus. The rate equation language of the latter is shown to be inappropriate. The decomposition probability is measured at constant fluence up to a pressure of 2 kPa and empirical representations of the pressure dependence of the MPD are reported. A collision-dependent reaction scheme is presented to explain the pressure dependence of the up-pumping through the vibrational manifold.
- Publication:
-
Journal of Chemical Physics
- Pub Date:
- May 1990
- DOI:
- 10.1063/1.458370
- Bibcode:
- 1990JChPh..92.5997M